ES2365641T3 - AMPHOTTER POLYMERS AS AN ADDITIVE FOR SOIL RELEASE (SOIL RELEASE) IN DETERGENTS. - Google Patents

Abstract

Use of water-soluble polymers at 20 ° C containing at least one polymerized monomer respectively a) H2C = CR 1 -CO-NH-R 2 -N + R 3 R 4 R 5 X - in which case R 1 represents a hydrogen atom or an alkyl residue with 1 to 4 atoms of C, R 2 represents an alkylene residue, linear or branched, with 1 to 12 atoms of C and R 3, R 4, R 5, independently of each other, they mean a hydrogen atom, an alkyl residue with 1 to 18 C atoms or a phenyl residue, and X - represents an anion of the group of halogens, sulfates and alkyl sulfates or hydroxide, phosphate, acetate, formate or ammonium, and b ) H2C = CR 6 -CO-NR 7 R 8 in which case R 6 represents a hydrogen atom or an alkyl residue with 1 to 4 atoms of C and R 7 and R 8, each independently of each other representing an atom of hydrogen, an alkyl residue with 1 to 4 C atoms or a C3-C6 cycloalkyl residue, with the proviso that R 7 and R 8 do not simultaneously represent a I take hydrogen, and c) acrylic and / or methacrylic acid and / you) other monomers of the C3-C6 carboxylic acid group, once ethylenically unsaturated, such as crotonic acid, maleic acid, maleic acid anhydride, fumaric acid, itaconic acid, as well as its hemiesters and salts, or H2C = CR-CO-NH-CR'R''R '' '- SO3H and its salts, mainly alkali metal and ammonium salts, in which case R, R ', R' 'and R' '', independently of each other, represent a hydrogen atom or an alkyl (en) residue or with 1 to 4 C atoms, with the proviso that the weight ratio to the polymer be from 20 to 30% by weight of monomer a), 50 to 70% by weight of monomer b) and 10 to 20% by weight of monomers c) and / od) with the additional condition that the sum of the fractions of how result 100, as an additive for soil release in soil detergents.

Description

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The present application relates to an additive for detergents, in which case this additive improves the release of dirt from the fibers or surfaces and / or prevents or decreases a new fouling, as well as detergents containing such polymers.

Detergents regularly contain, in addition to the essential ingredients for the washing process, such as surfactants and detergent builder materials, other components that can be grouped under the term auxiliary washing substances and which thus comprise different groups of active substances , such as foam regulators, crush inhibitors, bleaches, bleach activators and color transfer inhibitors. Auxiliary substances of this type also include substances that confer dirt repellent properties to the fibers of the laundry to be washed and, if present during the washing cycle, support the ability to release dirt from the other detergent components. In this case, these polymers are applied to the fibers by a first washing process and then simplify the washing process from now on thanks to a reduced adhesion of the dirt. As long as it is always washed with the polymer, the effect is also preserved. The same is valid by analogy also for hard surface cleaning products. Substances of this type that make it possible to remove dirt are often referred to as "soil-release" active substances or because of their ability to provide treated surfaces, such as fibers, with dirt repellency, they are called " soil-repellents. " A large number of chemical compounds that are suitable as soil-release additives can be inferred from the state of the art. Thus, EP 253 567 describes, for example, soil-release polymers with a molar mass of 900 to 9000 of ethylene terephthalate and polyethylene oxide terephthalate, in which case the polyethylene glycol units have molecular weight of 300 to 3000 and the molar ratio between ethylene terephthalate and polyethylene oxide terephthalate is 0.6 to 0.95. From DE 101 52 308 A1, polymeric compositions of polyisocyanates with polymeric polyols are known as soil release additives for cotton fibers.

All polymers of the prior art have a very specific and very narrow spectrum of action inherent; that is to say, they act either only in certain tissues or only in the face of certain soils. Therefore, there is a continuous demand for new soil-release additives, with the widest possible spectrum of action. A particular demand is seen in the case of soils containing oil and / or grease, for example motor oil and mainly in the case of soils on mixed fabrics (cotton / synthetic) or on pure cotton, since dirt of this type It can be removed only in a difficult way by using detergents.

It was found that certain water-soluble amphoteric terpolymers can solve the problem.

A first object of the present application therefore refers to the use of water-soluble polymers at 20 ° C, which contain at least one polymerized monomer respectively

a) H2C = CR1-CO-NH-R2-N + R3R4R5 X-

in which case R1 represents a hydrogen atom or an alkyl residue with 1 to 4 C atoms, R2 represents a linear or branched alkylene residue with 1 to 12 C atoms and R3, R4, R5 independently of each other mean a hydrogen atom, an alkyl residue with 1 to 18 C atoms or a phenyl residue, and X - represents an anion from the group of halogens, sulfates and alkyl sulfates or hydroxide, phosphate, acetate, formate or ammonium, and

b) H2C = CR6-CO-NR7R8

in which case R6 represents a hydrogen atom or an alkyl residue with 1 to 4 C atoms and R7 and R8, each, independently of each other, represents a hydrogen atom, an alkyl residue with 1 to 4 C atoms or a C3-C6 cycloalkyl residue, with the proviso that R7 and R8 are not simultaneously a hydrogen atom, and

c) acrylic and / or methacrylic acid and / or

d) other monomers of the C3-C6 carboxylic acid group, ethylenically unsaturated once, such as crotonic acid, maleic acid, maleic acid anhydride, fumaric acid, itaconic acid, as well as their hemiesters and salts, or H2C = CRCO- NH-CR'R "R" '- SO3H and its salts, mainly alkali metal and ammonium salts, in which case R, R', R "and R '", independently of each other, represent a hydrogen atom or an alkyl (en) residue or with 1 to 4 C atoms, with the proviso that the proportion by weight with respect to the polymer is from 20 to 30% by weight of monomer a), 50 to 70% by weight of monomer b) and 10 to 20% by weight of monomers c) and / od) with the other condition that the sum of the fractions results in 100, as a soil-release additive for detergents.

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The polymers corresponding to the description above are subject to the previous European application EP 176 7 554 of the applicant. This application also describes, by the way, a use of polymers to prevent re-fouling, however only with respect to hard surfaces, that is, for example, in dishwashing products. But this does not anticipate the specific use, now claimed, for detergents. For the use according to the invention, those polymers according to the above description whose weight fraction of monomers c) are less than 15% by weight and mainly equal to or less than 10% by weight are preferred. A preferred weight range for monomer c) is 5 to 25, preferably 5 to 15 and mainly 5 to 10% by weight, each case with respect to the total weight of the polymer. The polymers to be used according to the invention contain as polymerized monomers at least three different monomers from each other a) to d). All polymers containing adjacent are included herein, either the monomeric building blocks a), b) and c), or a), b) and d) or a), b), c) and d). It is also possible in the sense of the present invention to employ mixtures of the listed polymers.

Monomer components a)

Monomers of this type follow the general formula

H2C = CR1-CO-NH-R2-N + R3R4R5X

in which case R1 represents a hydrogen atom or an alkyl residue with 1 to 4 C atoms, R2 represents a linear or branched alkylene residue with 1 to 12 C atoms and R3, R4, R5, independently of each other, mean a hydrogen atom, an alkyl residue with 1 to 18 C atoms or a phenyl residue, and X represents an anion of the group of halogens, sulfates and alkylsulfates, represents hydroxide, phosphate, acetate, formate or ammonium. Particularly preferred are those monomers of type a), in which R1 represents a methyl residue, R2 represents a group CH2-CH2-CH2, and residues R3, R4 and R5 respectively represent a methyl residue. X-represents a suitable counter-ion, such as halide, hydroxide, sulfate, hydrosulfate, phosphate, formate or acetate, preferably chloride. These are known to the person skilled in the art under the name 3trimethylammoniumpropylmethacrylamidechloride (MAPTAC).

Monomer component b)

The second monomeric building block, mandatorily contained in the polymer of the invention, is an ethylenically unsaturated nitrogen-containing compound of the following general formula:

H2C = CR6-CO-NR7R8

in which case R6 represents a hydrogen atom or an alkyl residue with 1 to 4 C atoms and R7 and R8, each independently of each other, represent a hydrogen atom, an alkyl residue with 1 to 4 C atoms

or a C3-C6 cycloalkyl residue, with the proviso that R7 and R8 do not simultaneously represent a hydrogen atom. In this way it is alkylacrylamides. Particularly preferred is N-isopropylacrylamide, also known under the abbreviation NIPAM.

Monomer component c)

As the third component c) ethylenically unsaturated acids and salts thereof, such as acrylic and methacrylic acid, are suitable. Acrylic acid (AA) is on this occasion the particularly preferred monomer. Its alkali metal and ammonium salts represent particularly suitable salts.

Monomer component d)

As building blocks, other monomers may be additionally or instead of component c) in the polymers according to the invention. They are selected from the group of once-ethylenically unsaturated C3-C6 carboxylic acids, such as crotonic acid, maleic acid, maleic acid anhydride, fumaric acid, itaconic acid, as well as their hemiesters, and salts or H2C = CR-CO- NH-CR'R "R" 'SO3H and its salts, mainly alkali metal and ammonium salts, in which case R, R', R "and R" ', independently of one another, represent a hydrogen atom or an alkyl (en) residue or with 1 to 4 C atoms. A particularly preferred monomeric building block of type d) is in this case the molecule with the general formula H2C = CR-CO-NH-CR'R "R '"-SO3H, in which case a derivative, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), should be highlighted.

The polymers of the present invention are water soluble, that is, that at least 0.1 g of the polymer is soluble in 100 ml of water at 20 ° C. The polymers are ampholytic, that is to say that the polymers have both acidic and basic hydrophilic groups and behave acidic or basic depending on the condition.

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The polymers according to the invention preferably have an average molecular weight (weight average molecular weight, Mw), measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC-MALLS), in the range of 10,000 to 500,000 Da. The molecular mass of the polymers is preferably between 50,000 and 350,000 Da and mainly between 100,000 and 250,000 Da. A particularly preferred range can be between 110,000 and 140,000 Da. The different monomeric building blocks a) to d) preferably appear in certain proportions of selected adjacent quantities. Polymers containing component b) in excess (both with respect to mol and also the weight of the components) to components a) and c) are respectively preferred. Polymers are preferred here in which the molar ratio between monomers a), b) and c) is in the range of up to 5: 10: 5 and preferably in the range of 4: 10: 1 to 4: 10: 3 and mainly in the range of 3: 8: 2 to 3: 8: 1. Regarding the molar% of each of the monomers are contained 20 to 30% of monomer a), 50 to 70% of monomer b) and 10 to 20 % of monomer c). Provided that instead of component c) the monomeric building block of type d) is contained, the same proportions are analogously valid. But polymers containing adjacent monomers of both type c) and also type d) may be particularly preferred. Then, the monomeric construction units c) and d) are preferably adjacent in a molar ratio of 2: 1 to 1: 2, but particularly preferable in a ratio of 1: 1. Particularly preferred polymers with four distinct monomeric building blocks have in this case molar proportions a): b): c): d) from 2: 4: 1: 1 to 1: 10: 1: 1. A particularly preferred ratio is found in 3: 8: 1: 1. Preferred polymers are mainly those in which monomer a) is selected from those compounds of the general formula in which R 1 represents a methyl group, R 2 represents an alkylene residue with 3 atoms of C, R 3, R 4 and R 5 respectively represent methyl residues and X represents chloride , monomer b) is selected from those compounds of the general formula in which R6 and R7 represents a hydrogen atom and R8 represents an isopropyl residue and monomer c) is acrylic acid. In addition, polymers are preferred in which monomer a) is selected from those compounds of the general formula in which R 1 represents a methyl group, R 2 represents an alkylene residue with 3 atoms of C, R 3, R 4 and R 5 respectively represent methyl residues and X represents chloride, monomer b) is selected from those compounds of the general formula in which R6 and R7 represents a hydrogen atom and R8 represents an isopropyl residue and monomer c) represents H2C = CRCO-NH-CR ' R "R" '- SO3H and its salts, mainly alkali metal and ammonium salts, in which case R, R', R "and R" ', independently of one another, represents a hydrogen atom or a residue of alkyl (en) or with 1 to 4 atoms of C.

Such polymers to be used according to the invention can be prepared by polymerization methods that are known to the person skilled in the art. They can be prepared, for example, by solution polymerization or mass polymerization. Preferably they are prepared by solution polymerization, that is to say a polymerization of monomers in solvents and / or water, in which both the monomers and the polymers resulting therefrom are soluble. In addition, the polymerization can be carried out by loading the total amount of monomer or feeding the monomers in batches, semi-continuously or continuously. The polymerization is preferably carried out as batch polymerization with or without feeding the monomers.

A particularly preferred object of the present invention is the use of a water soluble polymer at 20 ° C which contains at least three different monomers a), b), c) and / od), in which case as monomers a) are select 3-trimethylammoniumpropylmethacrylamide chloride (MAPTAC), as monomers b) select Nisopropylacrylamide (NIPAM), as monomers c) select acrylic acid (AA) and / or methacrylic acid (MA), as monomers d) select acid 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS). According to the description above, those polymers whose fraction by weight of monomers c) are less than 15% by weight and mainly equal to or less than 10% by weight are preferred. A preferred weight range for monomer c) is 5 to 15 and mainly 5 to 10% by weight, each relative to the total weight of the polymer as a soil-release additive in detergents.

These polymers can also be described by the following formula scheme:

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The indices m, n, p and q reflect the amount of monomeric building blocks NIPAM, MAPTAC, AA and AMPS in the polymer molecule. However, the succession of the building blocks in the polymers of the invention, in general, is not necessarily fixed, rather all the successions of the individual building blocks are understood, be they blocks of the individual monomers or their succession purely random in the molecule. In the case of this previously defined type of polymer, those derivatives containing the polymerized MAPTAC, NIPAM and AMPS monomers in weight ratios of 25 to 50% of MAPTAC, 40 to 75% NIPAM and 1 to 15% of AMPS are particularly preferred, with the proviso that the sum of the percentage fractions of how 100 resulted. A polymer also preferably used independently of this is one containing the polymerized MAPTAC, NIPAM and AA monomers in weight ratios from 25 to 50% of MAPTAC, 40 to 75% of NIPAM and 1 to 15% of AA with the proviso that the sum of the percentage fractions results in 100. Finally, independently of the above, a water soluble polymer at 20 ° C containing the compounds is also preferred. MAPTAC, NIPAM, AA and AMPAS onomers in weight ratio from 25 to 45% MAPTAC, 40 to 70% NIPAM, 1 to 15% AA and 1 to 15% AMPS, provided that the sum of the percentage fractions gives 100 as a result ado. The preferred molar proportions described above as well as the preferred weight ratios of the monomers within the polymers are also valid for these polymers, that is to say that the molar ratio between monomers a), b) and c) or d) is in the range from 1: 10: 1 to 5: 10: 5 and preferably in the range of 4: 10: 1 to 4: 10: 3 and mainly in the range of 3: 8: 2 to 3: 8: 1. A polymer in particular Preferred contains the monomers a), b), c) and d) in a molar ratio of 3: 8: 1: 1. The weight ratio with respect to the polymer is 20 to 30% by weight of monomer a), 50 to 70% by weight of monomer b) and 10 to 20% by weight of monomers c) and / od) with the proviso that the sum of the fractions yields 100. Monomers c) and d), provided they are present adjacent to the polymers, are preferably in a weight ratio of 1: 1. The average molar weight of the selected polymers is, as described in detail above, preferably in the range of 10,000 to 500,000.

The polymers according to the above-mentioned description are added as additives to detergents per se known, which may be solid or liquid. In such a case, amounts between 0.01 to 10% by weight and mainly 0.05 to 10% by weight are particularly preferred. Most preferably, the range of 0.05 to 5% by weight, mainly 0.1 to 1.5% by weight, is preferred.

The detergents may contain, together with the polymers, other auxiliary materials and additives customary for detergents, for example surfactants (anionic, non-ionic, cationic and / or amphoteric surfactants), detergent or builder builders, other detergents complexing, enzymes, bleaching and bleaching activators or bleaching reinforcements, armor substances, perfumes and dyes, foam activators or foam inhibitors, non-aqueous solvents, disinfectants, optical brighteners, color transfer inhibitors, etc.

As surfactants, anionic and non-ionic surfactants are of major importance. Typical examples of anionic surfactants are alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, alpha-ethyl ester sulphonates, sulfo-fatty acids, alkyl sulfates, ether sulfates fatty acid, mixed hydroxyl ether sulfates, (ether) monoglyceride sulfates, fatty acid (ether) amide sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, isethionates of fatty acid, fatty acid sarcosinates, fatty acid taurides, N-acyloamino acids, such as, for example, acylolactylates, acylotartrates, acyloglutamates and acylopartates, alkyl oxyglucoside sulfates, protein fatty acid condensates (mainly wheat-based plant products) and alkyl (ether) phosphates. As long as the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably narrow, homolog distribution.

In this case, alkyl and / or alkenyl ether sulfates are preferably selected. The alkyl and / or alkenyl ether sulfates that are taken into consideration as component (b), represent sulfation products of linear fatty alcohols or partially branched oxoalcohols, known and obtainable on an industrial scale. In such a case, these preferably follow the formula (la),

RO (CH2CH2O) nSO3X (Ia)

wherein R represents a linear or branched alkyl and / or alkenyl residue with 6 to 22 carbon atoms, n represents numbers from 1 to 10 and X represents alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucamonium . Ether sulfates of the named type are prepared on an industrial scale by sulfation and neutralization following the corresponding polyglycol alcohol ethers. Typical examples are sulfates based on addition products of 1 to 10 and mainly 2 to 5 mol of ethylene oxide to capronic alcohol (hexanol), caprylic alcohol (octanol), 2-ethylhexyl alcohol, caprinic alcohol (decanol), alcohol lauryl (dodecanol), isotridecyl alcohol, myristyl alcohol (1-tetradecanol), cetyl alcohol (1-hexadecanol), palmolethyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolinyl alcohol,

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linolenyl alcohol, elaeostearyl alcohol, arachidic alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brasidyl alcohol, as well as their industrial mixtures in the form of sodium, potassium or magnesium salts.

Another preferred class of selected anionic surfactants represent alkylbenzenesulfonates (ABS). These preferably follow the formula (Ib)

R’-Ph-SO3X (Ib)

wherein R 'represents a branched alkyl residue, although preferably linear with 10 to 18 carbon atoms, Ph represents a phenyl residue and X represents an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucamonium. Preferably dodecylbenzene sulphonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates are used, as well as their industrial mixtures in the form of sodium salt.

In addition to the alkyl and / or alkenyl ether sulfates or ABS preferably used, as anionic surfactants may also be contained in the products of the invention additionally, or instead thereof, soaps, preferably sodium and potassium soaps. Ethanolamine salts are also suitable. In this case, amounts between 1 to 45% by weight, preferably 1 to 40% by weight and mainly 30% by weight, preferably up to 15% by weight (each case with respect to the total amount of detergent) are preferred. Preferably, potassium soaps or, particularly preferably, C12-C18 fatty acid sodium soaps are used.

In addition, the joint use of non-ionic surfactants is possible and preferable. A particularly preferable type of non-ionic surfactants represent those of the alkyl (oligo) glycoside, fatty alcohols and / or alkoxylated fatty alcohols, preferably ethoxylated, class. Alkyl and alkenyl oligoglycosides represent known non-ionic surfactants that follow formula (II),

R1O- [G] p (II)

wherein R1 represents an alkyl and / or alkenyl residue with 4 to 22 carbon atoms, G represents a sugar residue with 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant methods of the preparative organic chemistry. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably from glucose. Preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglycosides. The index number p in the general formula (II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides and represents a number between 1 and 10. While p must always be an integer in a compound given and here first of all p can assume the values = 1 to 6, the p-value for a given alkyl oligoglycoside is an analytically determined quantity calculated that most often represents a fractional number. Preferably, alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are used. From an industrial application point of view, those alkyl and / or alkenyl oligoglycosides are preferred, their degree of oligomerization is less than 1.7 and is mainly between 1.2 and 1.4. The alkyl or alkenyl residue R 1 may be derived from primary alcohols with 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caprylic alcohol, caprylic alcohol, caprylic alcohol and undecyl alcohol as well as their technical mixtures, as obtained, for example, by hydrogenating industrial fatty acid methyl esters or in the development of hydrogenation of aldehydes from the Roelen oxosynthesis. Alkyl (oligo) glycosides of the C8-C10 chain length (DP = 1 to 3) are preferred, which are obtained as head in the distillation of industrial C8-C18 coconut fatty alcohol distillation and may have impurities of a fraction of less than 6% by weight of C12 alcohol as well as C9 / 11 alkyl oxoglycosides based on industrial oxoalcohols (DP = 1 to 3). The alkyl or alkenyl residue

R1

it can also be derived in addition to primary alcohols with 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmolethyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachidic alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brasidyl alcohol as well as their industrial mixtures, which can be obtained as described above. C12 / 14 hydrogenated coconut alcohol based alkyloligoglycosides with a DP of 1 to 3 are preferred.

For reasons of preparation, alcohol ethoxylates are referred to as fatty alcohol ethoxylates or oxoalcohol and preferably follow the formula (III),

R2O (CH2CH2O) nH (III)

wherein R2 represents a linear or branched alkyl and / or alkenyl residue with 6 to 22 carbon atoms and n represents numbers from 1 to 50, in which case the range may be particularly preferable from 3 to 30 and mainly from 3 to 12. Typical examples are the addition products of 1 to 50 on average, preferably 5 to 40 and mainly 10 to 25 mol to, for example, capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, caprinic alcohol, lauryl alcohol, isotridecyl alcohol, alcohol myristyl, cetyl alcohol, palmoleyl alcohol, alcohol

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stearyl, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachidic alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brasidyl alcohol, as well as their industrial mixtures that are obtained, for example, by hydrogenating high-pressure industrial methyl ethers to base of fats and oils or aldehydes of Roelen oxosynthesis, as well as fraction of monomers when dimerizing unsaturated fatty alcohols. Addition products of 10 to 40 mol of ethylene oxide to industrial fatty alcohols with 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fat alcohol, are also preferred.

As surfactants, together with the substances described above, all other nonionic, anionic, cationic and / or amphoteric, known to those skilled in the art, may also be contained. Typical examples of non-ionic surfactants are polyglycol ethers of fatty alcohol, polyglycol ethers of alkylphenol, polyglycol esters and fatty acid, polyglycol ethers of fatty acid, polyglycol ethers of fatty amine, alkoxylated triglycerides, mixed and formal ethers mixed, partially oxidized alkylo-glycosides and glucoronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates (mainly wheat-based plant products), fatty acid and polyol esters, sugar esters, sorbitol esters, polysorbates and amino acids. As long as the non-ionic surfactants contain polyglycol ether chains, they can have a conventional homolog distribution, although preferably a narrow one.

Typical examples of cationic surfactants are quaternary ammonium compounds and esterquats, mainly quaternary salts of trialkanolamine esters and fatty acid. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkylamido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfo betaines. The surfactants mentioned are exclusively known compounds.

Preferably, those products containing non-ionic surfactants are used in amounts of 1 to 35% by weight, preferably 5 to 25% by weight and mainly 5 to 20% by weight. Another additional component may be advantageously soap, in which case it may be advantageously contained in amounts of 1 to 40% by weight, preferably 10 to 38% by weight and mainly 12 to 38% in weight. weight with respect to the total weight of liquid products. In addition it may be advantageous that the products according to the description above are free of cationic surfactants and mainly free of cationic textile softeners. With particular advantage, in this case, those products containing a mixture of surfactants that are composed of anionic surfactants (other than soaps), alkyl (oligo) glycosides and alkoxylated fatty alcohol in the preferred weight ratio of 1: 1 are selected: 4 to 1: 1: 2. If there is soap content, then in a ratio of preferably 4: 1 with respect to those also present, other anionic surfactants. It is also valid that mixtures of surfactants containing anionic and / or non-ionic surfactants in amounts of, in total, 50 to 90% by weight are preferred.

Without being associated with a given theory, with respect to the principle of action of the soil-release additive, the applicant is based on the fact that the polymers to be used according to the invention during the washing of the textiles pass from the detergents first to the aqueous liquid of washed and from there then adhere to the fibers and on the surface of the fibers a thin polymeric film is formed which then, after drying the washed object, remains there and prevents or decreases more fouling, especially when it is used again in each additional wash cycle a polymer containing detergent.

Another object of the invention is therefore directed to a method for temporarily providing textiles (ie not permanently, as they are used in the manufacture of textiles and their refining) of a soilrelease additive (for soil release), in which In a first step, the textile is contacted in an aqueous lye with a product containing polymers according to the description above, as well as optionally surfactants and other ingredients, in which case, in a second step, the aqueous lye is heated to a temperature of at least 30 ° C together with textile, and then the textile dries; Optionally, the textile can be contacted with clean water before drying. The method is preferably carried out in washing machines, preferably in those for private consumption, that is to say in domestic washing machines. In such a case with the polymers of the invention all the usual fiber materials can be treated, as they are used for washing. Cotton textiles, mainly pure cotton, mixed cotton / synthetic fabrics or synthetic pure fabrics, are preferred, in which case cotton and / or mixed cotton / synthetic fabrics are particularly preferred. Synthetic fibers are mainly those of polyester. The polymers to be used in accordance with the present invention show a particularly advantageous effect by preventing re-fouling with dirt containing oil and / or grease, for example motor oils or similar soils.

Particularly preferred is the use of the polymers of the invention in detergents that can be solid or liquid. Detergents here are mainly those products that are used for washing textiles and preferably garments, preferably domestic clothes.

Another object of the invention therefore relates to a liquid detergent containing a) 0.05 to 10% by weight, and preferably 0.05 to 5% by weight of a polymer according to the description above, as well as b) 5 at 45% by weight of surfactants and c) at least 16% by weight of water, as well as optionally d) other auxiliaries and additives. Such products are described, however, by adding a specific color transfer inhibitor in EP 1 645

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619 A1. The joint use of soil-release polymers in the context of the present industrial disclosure cannot be inferred from the document. But the joint use of polydiallyldimethylammonium chlorides or their derivative can be discarded for the products (solids and liquids) of the present invention.

The surfactant component b) is preferably composed herein of the types described above. Liquid detergents may also have, together with the named surfactants, other typical ingredients, such as solvents, hydrotropes, bleaching agents, builder detergents, viscosity regulators, enzymes, enzyme stabilizers, optical brighteners, other repellents. dirt (soil repellents) other than polymers according to the invention (but it is preferred that for this purpose only the polymers of the invention be contained), foam inhibitors, inorganic salts as well as fragrant substances and dyes, with the condition that these are sufficiently stable to storage in this aqueous medium. Organic solvents include, for example, mono- and / or polyfunctional alcohols with 1 to 6 carbon atoms, preferably with 1 to 4 carbon atoms. Preferred alcohols are ethanol, 1,2-propanediol, glycerin and mixtures thereof. The products preferably contain 2 to 20% by weight and mainly 5 to 15% by weight of ethanol or any mixture of ethanol and 1,2-propanediol or mainly of ethanol and glycerin. It is also possible that the preparations contain, in addition to the mono- and / or polyfunctional alcohols with 1 to 6 carbon atoms, or alone, polyethylene glycol with a relative molecular mass between 200 and 2000, preferably up to 600 in amounts of 2 at 17% by weight. As hydrotropes, for example, toluene sulphonate, xylene sulphonate, cumene sulphonate or mixtures thereof can be used. Among the compounds that supply hydrogen peroxide in water, which serve as bleaches, sodium perborate tetrahydrate and sodium perborate monohydrate have a particular meaning. Other bleaches are, for example, peroxycarbonate, citrate perhydrate as well as peracids, such as perbenzoates, peroxyphthalates or diperoxidedecandioic acid. They are usually used in amounts of 8 to 25% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and mainly 10 to 15% by weight is preferred. Because of its ability to bind free water forming the tetrahydrate, it helps to increase the stability of the product. However, the preparations are preferably free of bleach of this type. Suitable detergent builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, such as the neutral reacting salt of 1-hydroxyethane-1,1, diphosphonate, which may be present in amounts of 0 , 5 to 5, preferably 1 to 2% by weight. As viscosity regulators, for example hydrogenated castor oil, salts of long chain fatty acids, which are preferably used in amounts of 0 to 5% by weight and mainly in amounts of 0.5 to 2% by weight, for example, for example sodium, potassium, aluminum, magnesium and titanium stearate or sodium and / or potassium salts of behenic acid, as well as other polymeric compounds. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example polyacrylates, homopolymeric or copolymeric polymethacrylates, and mainly copolymers of acrylic acid with maleic acid, preferably those of 50% to 10% maleic acid. The relative molecular mass of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably between 50,000 to 1200,000, with respect to the free acid. Also suitable are mainly water-soluble polyacrylates which intersect, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular mass above one million. Examples of these are the polymers available under the name Carbopol 940 and 941 with thickening action. Crosslinked polyacrylates are preferably used in amounts not above 1% by weight, preferably in amounts of 0.2 to 0.7% by weight. The products may additionally contain about 5 to 20% by weight of a partially esterified copolymer. These partially esterified polymers are obtained by copolymerization of (a) at least one C4-C28 olefin or mixtures of at least one C4-C28 olefin with up to 20 mol% of C1-C28 alkylvinyl ethers and (b) anhydrides of ethylenically unsaturated dicarboxylic acid with 4 to 8 carbon atoms in 1: 1 molar ratio to copolymers with K values of 6 to 100 and then partial esterification of the copolymers with reaction products such as C1-C13 alcohols, C8-fatty acids C22, C1-C12 alkylphenols, secondary C2-C30 amines or mixtures thereof with at least one C2-C4 alkylene oxide or tetrahydrofuran as well as hydrolysis of anhydride groups of the copolymers to give carboxyl groups, in which case esterification partial copolymers are conducted until 5 to 50% of the carboxyl groups of the copolymers have been esterified. Preferred copolymers contain ethylenically unsaturated dicarboxylic acid anhydride to maleic acid anhydride. The partially esterified copolymers may be present either in the form of the free acid or preferably partially or totally neutralized. The copolymers are advantageously employed in the form of an aqueous solution, mainly in the form of a solution of 40 to 50% by weight. The copolymers make not only a contribution to the primary and secondary washing power of the liquid detergent and the liquid cleaner, but also causes a desired decrease in the viscosity of the concentrated liquid detergent. By using these partially esterified copolymers, concentrated aqueous liquid detergents are obtained that are capable of flowing under the sole influence of the force of gravity and without the action of other cutting forces. Concentrated aqueous liquid detergents contain partially esterified copolymers in amounts of 5 to 15% by weight and mainly in amounts of 8 to 12% by weight. Enzymes are considered those of the class of proteases, lipases, amylases, cellulases and mixtures thereof. The preparation of such liquid detergents is carried out in processes known to the person skilled in the art, preferably by stirring the ingredients optionally at elevated temperatures. The pH value of such products is in general from 7 to 10.5, preferably 7 to 9.5 and mainly 7 to 8.5. The adjustment of higher pH values, for example above 9, can be done by using small amounts of sodium hydroxide or alkaline salts such as sodium carbonate or sodium silicate. Liquid detergents of the invention generally have viscosities.

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between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C). Here, viscosities between 150 and 5000 mPas are referred to in the products. The viscosity of the aqueous products is preferably below 2000 mPas and is mainly between 150 and 1000 mPas.

Also subject to the present industrial disclosure is a solid detergent containing a) 0.05 to 10% by weight, and preferably 0.05 to 5% by weight of a polymer according to the description above, b) 2 to 20% in surfactant weight c) 0.05 to 10% by weight of water, as well as optionally d) other auxiliary and additive substances. As auxiliary substances in solid detergents that can generally be formulated as powder, granulate, extrudate or molded bodies, for example tablets, they should be named primarily builder (detergent boosters), bleach and bleach activators. As a solid builder, mainly finely crystalline, synthetic zeolite containing bound water is used, such as NaA zeolite for detergents. Although zeolite NaX as well as mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or also as a stabilized suspension, not dried, still wet from its preparation. Among the compounds that provide hydrogen peroxide in water, which serve as bleaches, sodium perborate tetrahydrate and sodium perborate monohydrate have a particular significance. Other bleaches are, for example, peroxycarbonate, citrateperhydrate as well as salts of peracids, such as perbenzoates, peroxyphthalates or diperoxidedecandioic acid. It is usually used in amounts of 8 to 25% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and mainly 10 to 15% by weight is preferred. Thanks to its ability to bind free water forming the tetrahydrate, it helps to increase the stability of the product. To achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl and O-acyl compounds that form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, in addition to carboxylic acid anhydrides and polyol esters such as glucose pentaacetate. The content of bleach activators in the product containing bleach is in the usual range, preferably between 1 and 10% by weight and mainly between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ’, N’-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine.

The solid detergents can be prepared according to any known process, such as mixing, spray drying, granulation and extrusion. Mainly suitable are those processes in which the partial components are mixed together, for example spray dried components and granulated and / or extruded components. In such a case it is also possible to load the spray-dried or granulated components later in the conditioning with non-ionic surfactants, mainly ethoxylated fatty alcohols, for example, according to the usual methods.

Examples

Three liquid detergents were prepared where one without (M1), one with (M2) a soil-release additive (Repellotex: Rhodia company) of the prior art and a product of the invention (E1) were compared to each other. As polymer in the context of the invention it was prepared as follows: 12.4 g of MAPTAC, 1.4 g of acrylic acid and 50 g of water were mixed. The pH value of the aqueous mixture was installed in the range of 6.5 to 7.5. Then 8.5 g of NIPAM and 23 g of isopropanol were added and this mixture was heated to 65 ° C. Then 0.15 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added as the initiator and the reaction started. In this case the mixture is heated to approximately 80 ° C. After the reaction had elapsed, the water / isopropanol azeotrope was distilled at 80-100 ° C. The concentration of the resulting polymer solution was approximately 22% by weight. The pH value of the solution was 5 to 7.5. The polymer had a molecular weight of 130,000 Da (measured by means of SEC-MALLS).

The composition of liquid detergents is found in the following table:

Active substance% by weight

M1 E1 M2

Water

53.8 52.8 52.8

NaOH

3.4 3.4 3.4

Soap

8.9 8.9 8.9

Propylene glycol

5.0 5.0 5.0

(continuation)

Sodium lauryl ether sulfate salt

3.4 3.4 3.4

C12-18 + 7-EO fatty alcohol

13.5 13.5 13.5

Alkyl (from C12-16) -1.4-glycoside

3.4 3.4 3.4

Polymer of the invention

- 1.0 -

Repellotex SRP-4

- - 1.0

Ethanol

3.0 3.0 3.0

Borax

0.2 0.2 0.2

Defoamer

0.4 0.4 0.4

NaCl

1.0 1.0 1.0

Citric acid

3.0 3.0 3.0

Biocide

0.1 0.1 0.1

Amylase

0.5 0.5 0.5

Protease

0.5 0.5 0.5

PH value

9.5 9.5 9.5

For the industrial application test, test textiles were washed in a domestic washing machine at 40 ° C, in which case the textiles had been provided with different test dirt, or were equipped after the washing cycle. The following table shows the results for the detergents described above:

The tissues (= test monitors) were pre-washed respectively 3 times with the formulation to be tested. The soils indicated were then applied to the tissue so treated so that a 2 cm round spot was generated for each dirt. The stained tissues were aged 1 week at room temperature. TO

Then they were washed again with the corresponding detergent. Conditions for this wash cycle:

Miele W 985

40 ° C color wash program

Water hardness = 14 ° dH

Load of laundry = 4 kg consisting of clean cotton IEC 456 and

15 4x dirt load wfk SBL 2004

Dosage WM = 75g / cycle

The washed test monitors were dried and ironed. Next, the Y value was determined for each spot with the help of a spectral photometer (Spectraflash 600 from Datacolor) using the UV suppressor filter FL 42 in daylight D 65. The indicated values are average values of 5 wash repetitions .

20 The higher the measured value, the better.

Washing power at 40 ° C after the 2nd. wash cycle:

Dirt

Fiber material * M1 E1 M2

Oily skin powder

PES 78.7 82.7 79.9

Frying fat

PES 86.4 87.4 86.7

Motor oil

PES / Co 35 41.2 35.5

Motor oil

PES 81.5 84 81.1

* PES = Polyester; PES / Co mixed fabric polyester / cotton

The results document the particular effectiveness of the polymers of the present invention against soils containing oil and grease.

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Claims (10)

1. Use of water-soluble polymers at 20 ° C containing at least one polymerized monomer respectively a) H2C = CR1-CO-NH-R2-N + R3R4R5 X- in which case R1 represents a hydrogen atom or an alkyl residue with 1 to 4 C atoms, R2 represents an alkylene residue, linear or branched, with 1 to 12 C atoms and R3, R4, R5, independently one of another means a hydrogen atom, an alkyl residue with 1 to 18 C atoms or a phenyl residue, and X represents an anion from the group of halogens, sulfates and alkyl sulfates or hydroxide, phosphate, acetate, formate or ammonium , Y b) H2C = CR6-CO-NR7R8 in which case R6 represents a hydrogen atom or an alkyl residue with 1 to 4 C atoms and R7 and R8, each independently of each other representing a hydrogen atom, an alkyl residue with 1 to 4 C atoms or a C3-C6 cycloalkyl residue, with the proviso that R7 and R8 do not simultaneously represent a hydrogen atom, and c) acrylic and / or methacrylic acid and / or d) other monomers of the C3-C6 carboxylic acid group, once ethylenically unsaturated, such as crotonic acid, maleic acid, maleic acid anhydride, fumaric acid, itaconic acid, as well as their hemiesters and salts, or H2C = CR -CO-NH-CR'R "R" '- SO3H and its salts, mainly alkali metal and ammonium salts, in which case R, R', R "and R '", independently of each other, represent a hydrogen atom or an alkyl (en) residue or with 1 to 4 C atoms, with the proviso that the proportion of weight with respect to the polymer is from 20 to 30% by weight of monomer a), 50 to 70% by weight of monomer b) and 10 to 20% by weight of monomers c) and / or d) with the additional condition that the sum of the fractions of how result 100, as an additive for soil release in soil detergents.

2.

Method to provide textiles with a soil-release polymer, characterized in that

a) the textile in an aqueous lye is contacted with a product containing polymers such as those used in claim 1, as well as surfactants and other ingredients, and then b) the aqueous lye is heated together with the textile at a temperature of at least 30 ° C, and then c) the textile is dried, in which case d) the textile can optionally be placed in contact with clean water before drying.

3.

Method according to claim 2, characterized in that it is carried out in a washing machine, preferably a domestic washing machine.

Four.

Method according to at least one of claims 1 to 3, characterized in that the textiles are made of cotton or synthetic fabrics, but preferably of cotton and / or mixed cotton / synthetic fabrics.

5.

Liquid detergent containing

a) 0.05 to 10% by weight, and preferably 0.05 to 5% by weight of a polymer as used in claim 1 b) 5 to 45% by weight of surfactants and c) at least 16% by weight of water, as well as optionally d) other auxiliary and additive substances.

6.

Product according to claim 5, characterized in that as component b) it contains a mixture of surfactants containing adjacent non-ionic surfactants, anionic surfactants and optionally soap.

7.

Product according to claim 6, characterized in that anionic surfactants are contained in amounts

0.5 to 70% by weight, preferably 0.5 to 50% by weight and mainly in amounts of 1 to 25% by weight, 5 with respect to the product.

8.

Product according to at least one of claims 5 to 7, characterized in that water is contained in amounts of 20 to 90% by weight, preferably 25 to 80% by weight and mainly 45 to 75% by weight.

9.

Solid detergent containing

a) 0.05 to 10% by weight, and preferably 0.05 to 5% by weight of a polymer as used in claim 1 10 b) 2 to 20% by weight of surfactants c) 0.05 to 10% by weight of water, as well as optionally d) other auxiliary and additive substances. 10. Use of polymers, such as those used in claim 1 as a soil-release additive, for application on pure cotton and / or mixed cotton / synthetic fabrics. fifteen